Polycarbonates are a type of engineering thermoplastic that have countless uses in modern society. Currently, the major industrial production of polycarbonates involves the polycondensation of a diol and phosgene or phosgene derivative. Though there are many advantages to this process, it creates large amounts of waste and requires dangerous chemicals in order to proceed. Over the past four decades, the coupling of CO_(2) and epoxides has grown into a viable, greener alternative for the production of select polycarbonates. The byproduct of this reaction, cyclic carbonates, also have use as polar, high boiling solvents. This dissertation will be divided into three parts. First, the coupling of indene oxide and CO_(2) to form poly(indene carbonate) and cis-indene carbonate will be discussed. Poly(indene carbonate) has the highest Tg yet reported for polymers derived CO_(2) /epoxides coupling, up to 138degreeC. Polycarbonate production requires the use of (salen)Co(III) catalysts and low temperatures, though some cyclic carbonate production is still observed. Selective production of poly(indene carbonate) has been achieved through the use of bifunctional cobalt(III) complexes. The effects of temperature and cosolvent choices on polymer production will be thoroughly discussed. Though polycarbonate is the kinetic product from the coupling of CO_(2) and epoxides, the thermodynamic product is cyclic carbonate. There are six potential mechanisms that yield this undesired byproduct, though there is limited research into which pathways are the most active during polymerization reactions. Temperature-dependent kinetic studies were performed to obtain the activation parameters for the direct, polymer-free coupling of cyclopentene oxide, indene oxide, 1,2-butylene oxide, and styrene oxide with CO_(2) utilizing (salen)CrCl/nBu_(4)NCl to yield their corresponding cyclic carbonates. Additionally, the metal-free backbiting of the singly-coupled styrene oxide/CO_(2) intermediate was simulated utilizing the halohydrin 2-chloro-1-phenylethanol. Finally, the coupling of cyclopentene oxide with carbon disulfide to yield poly[thio]carbonates and cyclic [thio]carbonates utilizing (salen)CrCl/PPNX will be discussed. In each reaction, scrambling of the oxygen and sulfur atoms in both the polymeric and cyclic product is observed. Long reaction times lead to increased amounts of [thio]ether linkages and therefore polymers with lower glass transition temperatures. Insights into both the coupling and scrambling mechanisms will be presented.

The nonlinear refractive index (n2) of room temperature liquid CS2 in the wavelength range of 9 to 11 micrometers is measured. A line tunable hybrid C02 TEA laser and amplifier system is used for the experiments. In these measurements the well known photoacoustic method is utilized to observe the onset of whole beam self-focusing. The photoacoustic signal in a CS2 cell, much longer than the confocal parameter, is monitored. The departure of the acoustic signal from linear growth marks the critical power for the onset of nonlinearity. It is experimentally verified that the phenomenon is power dependent as expected from self-focusing theory. The value of n2 is then calculated from the theoretical model of self focusing. Measurements of the on-axis irradiance transmitted through the nonlinear material as well as the measurements of beam distortion are used to verify the validity of the photoacoustic method. In all the measurements the on-axis intensity was smaller than the calculated threshold intensity for stimulated Brillouin scattering. The back reflection was monitored to make sure that stimulated Brillouin scattering was not playing a role in the phenomenon.

<p></p><p><a>COS and CS₂ are sulfur compounds that are formed in natural waters. These compounds are also volatile, which leads them move into the atmosphere and serve as critical precursors to sulfate aerosols. Sulfate aerosols are known to counteract global warming by reflecting solar radiation. One major source of COS and CS₂ stems from the ocean. While previous studies have linked COS and CS₂ formation in these waters to the indirect photolysis of organic sulfur compounds, much of the chemistry behind how this occurs remains unclear. This study examined this chemistry by evaluating how different organic sulfur precursors, water quality constituents, and temperature affected COS and CS₂ formation in natural waters.</a></p> <p>In the first part of this thesis (chapters 2 and 3), nine natural waters ranging in salinity were spiked with various organic sulfur precursors (e.g. cysteine, cystine, dimethylsulfide (DMS) and methionine) exposed to simulated sunlight over varying exposures. Other water quality conditions including the presence of O₂, CO and temperature were also varied. Results indicated that COS and CS₂ formation increased up to 11× and 4×, respectively, after 12 h of sunlight while diurnal cycling exhibited varied effects. COS and CS₂ formation were also strongly affected by the DOC concentration, organic sulfur precursor type, O₂ concentration, and temperature while salinity differences and CO addition did not play a significant role.</p> <p>To then specifically evaluate the role of DOM in cleaner matrices, COS and CS₂ formation was examined in synthetic waters (see chapters 4 and 5). In this case, synthetic waters were spiked with different types of DOM isolates ranging from freshwater to ocean water along with either cysteine or DMS and exposed to simulated sunlight for up to 4 h. Surprisingly, CS₂ was not formed under any of the tested conditions, indicating that other water quality constituents, aside from DOM, were responsible for its formation. However, COS formation was observed. Interestingly, COS formation with cysteine was fairly similar for all DOM types, but increasing DOM concentration actually decreased formation. This is likely due to the dual role of DOM on simultaneously forming and quenching the reactive intermediates (RIs). Additional experiments with quenching agents to RIs (e.g. ³DOM* and ·OH) further indicated that ·OH was not involved in COS formation with cysteine but ³DOM* was involved. This result differed with DMS in that ·OH and ³DOM* were both found to be involved. In addition, treating DOM isolates with sodium borohydride (NaBH₄) to reduce ketone/aldehydes to their corresponding alcohols increased COS formation, which implied that the RIs formed by these functional groups in DOM were not involved. The alcohols formed by this process were not likely to act as quenching agents since they have been shown to low in reactivity. Since ketones are known to form high-energy-triplet-states of DOM while quinones are known to form low-energy-triplet-states of DOM, removing ketones from the system further supported the role of low-energy-triplet-states on COS formation. This was initially hypothesized by findings from the testes on DOM types. In the end there are several major research contributions from this thesis. First, cysteine and DMS have different mechanisms for forming COS. Second, adding O₂ decreased COS formation, but it did not stop it completely, which suggests that further research is required to evaluate the role of RI in the presence of O₂. Lastly, considering the low formation yields of COS and CS₂ formation from the organic sulfur precursors tested in this study, it is believed that some other organic sulfur precursors are missing which are likely to generate these compounds to higher levels and this needs to be investigated in future research. </p><br><p></p>

Retention in Computer Science undergraduate education, particularly of underrepresented groups, continues to be a growing challenge. A theme shared by much of the research literature into why this is so is one of a distancing in the relationship between Computer Science professors and students [39, 40, 45]. How then, can we begin to lessen that distance, and build stronger connections between these groups in an era of growing class sizes and technology replacing human interaction? This work presents BitFit, an online programming practice and learning tool, to describe an approach to using the telemetry made possible from deploying this or similar tools in introductory programming courses to improve the quality of instruction, and the students' course experiences. BitFit gathers interaction data as students use the tool to actively engage with course material. In this thesis we first explore what kind of quantitative data can be used to help professors gain insights into how students might be faring in their courses, moving the method of instruction towards a data- and student-driven model. Secondly, we demonstrate the capacity of the telemetry to aid professors in more precisely identifying students at risk of failure in their courses. Our goal is to reveal possible reasons these students would be considered at-risk at an early enough point in the course to make interventions possible. Finally, we show how the use of tools such as BitFit within introductory programming courses could positively impact the student experience. Through a preliminary qualitative assessment, we seek to address impact on confidence, metacognition, and the ability for an individual to envision success in Computer Science. When used together within an all-encompassing approach aimed at improving retention in Computer Science, tools such as BitFit can move towards improving the quality of instruction and the students' experience by helping to build stronger connections rooted in empathy between professors and students. / Graduate / 0710 / 0984 / alrusso@uvic.ca

In this paper, we describe a recent trend in the introductory computer science curriculum which advocates conceptualizing computation primarily as coordinated concurrent activities [8], [9], [10]. Consistent with this philosophy is the focus on the event-driven model of computation [7]. While one can utilize these approaches with any thread and/or event supporting object-oriented language (e.g. Java) in a desktop programming environment, they become particularly worthwhile when used in conjunction with physical robots. This paper argues the case for the benefits of this approach and provides sample exercises that illustrate the use of this pedagogy using Lego Mindstorms RCX bricks programmed in Java for use in introductory programming.

No description available.

The synthesis of high molecular weight copolymer of carbon disulphide (CS2) and propylene oxide (PO) has not reported in literature. In the present work, zinc isopropyl xanthate (Zn(Xt)2) was used as catalyst for the copolymerisation of PO and CS2 into high copolymer. However, the product can be fractionated into high and low molecular weight components. High molecular weight copolymer was rubbery products, but low molecular weight copolymers were oily products containing cyclic dithiocarbonates. Copolymers were characterized by elemental, end group analysis, DSC, TGA, GPC, Light Scattering, UV, IR, NMR spectroscopy, polarized microscopy and refractometry. Copolymerization process was zeroth order with respect to monomers, and its non-terminated but suffered from several types of transfer reactions. As a result of transfer reactions S-(C=S)-S, O-(C=S)-O, O-(C=O)-O groups in the backbone of copolymer and SH groups at the chain terminals and cyclic dithiocarbonates are formed. Apart from SH groups, OH and double bonds were found and their amounts were determined at the chain terminals. Copolymers with high mole fractions of PO units (F1) in the copolymer are crystallized in the shape of Malta&amp / #8217 / s Cross. Melting points of products were obtained from DSC. The F1 values are calculated from elemental analysis as well as zeroth order rate constants and from melting point of the crystals. All three results were in close agreement and changed between 0.9 &amp / #8211 / 0.7. However, these ratios depend on reaction conditions (temperature, catalyst and monomer concentrations, time and dielectric constant of reaction medium). A mechanism for coordination-copolymerization on the basis of above observation was proposed.

No description available.